Process for dyeing textile materials in an aqueous bath containing a dyestuff in the presence of a trifunctional triazine



United States Patent 3,278,253 PROCESS FOR DYEING TEXTILE MATERIALS INAN AQUEOUS BATH CONTAINING A DYESTUFF IN THE PRESENCE OF A TRIFUNCTIONALTRI- AZINIE Gerhard Weckler and Siegfried Schiessler, Frankfurt am Main,Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormalsMeister Lucius & Briining, Frankfurt am Main, Germany, a corporation ofGermany No Drawing. Filed Aug. 20, 1963, Ser. No. 303,425 Claimspriority, application Germany, Aug. 22, 1962, F 37,646 9 Claims. (Cl.8-17) This invention relates to improvements in the dyeing of textilematerials such as yarns, filaments, fibers and fabrics having a basis ofsynthetic linear polyamides, as, for example, nylon. More particularly,the present invention relates to an improved process for dyeing yarns,filaments, fibers and fabrics made of, or essentially consisting of,synthetic linear polyamides with acid dyestuffs, complex metal dyestuffsor reactive dyestuffs or mixtures thereof.

It is well known in the art that textile materials made from polyamidescan be dyed with various dyestuffs, for example, with acid wooldyestuffs, metal complex dyestuffs or chrome dyestuffs, at temperaturesbelow and above 100 C. However, the dyeings thus produced are notsatisfactory, because in most cases it is not possible to levelirregularities of the yarn which are mainly caused by variations of thetiter and differences in stretching and fixing. These yarnirregularities are distinctly visible after dyeing as streaks, bands orin the form of an unsettled appearance, depending on the type of goods,and they considerably reduce the sales value of the goods.

To by-pass these drawbacks, it has been proposed, in addition toselecting a suitable dyestuff, to retard'the dyeing process and to carryit out in the presence of swelling agents in order to augment thepenetration into the fiber, and thus to prevent blocking effects. Asswelling agent-s, there have been used, for example, phenols andchlorinated, aromatic substances. These products, however, involve anumber of disadvantages. They are, in most cases, not simple to use andthey are effective only in high concentrations. In addition, they arepartly strongly absorbed by the fibers so that they can be removed lateron with difficulty only and may then cause damage to the fibers.Although they reduce streakiness, they do not totally remove thestreaks.

Furthermore, attempts have also been made to produce level dyeingsthrough control of the substantivity of the dyestuff by shifting thepH-value of the dyebath during dyeing by the addition of a potentiallyacid dyeing assistant to the bath. However, this process does not removeor level streakiness of the fabric dyed.

Furthermore, it is known to use surface-active agents in the dyeing ofpolyamide fibers. Attempts have been made to produce level dyeings byadding cation-active dyeing assistants to the dyebath which are capableof forming complexes with acid wool dyestuffs, and to retard theirpenetration into the fiber. This process, too, does not yieldsatisfactory results, because the cation-active products tend toprecipitate the acid dyestuffs. Even the addition of non-ionicdispersing agents to the dyebath does not remove the difficulties anddoes not offer the required reliability. Furthermore, there has beendescribed the use of anion-active products which are added to thedyebath and which are to compete with the dyestuff for the free linkingpositions of the fibers. However, these products possess either suchstrong aflinity for the polyamide fiber that all linking positions ofthe fiber are occupied by the dyeing assistant and that the dyebathscannot be ex- 3,278,253- Patented Oct. 11, 1966 hausted, or they arewell able to retard the penetration of the acid dyestuff into thepolyamide fiber in the case of light dyeings, but do not satisfactorilylevel out the streakmess.

Furthermore, products are described in the literature which are acombination of special, anion-active substances with complex-forming,weakly cation-active surface-active compounds such as polyvinylpyrrolidone, or hydroxyethylated aminophenols.

In many cases these products are capable of levelling out thestreakiness occurring with polyamide fibers when dyeing with aciddyestuffs; in the case of difficult dyeings with acid dyestuffcombinations, they exhibit retarding effects which are different foreach component of the dyestuff combination, so that dyestuff losses andalterations of shade are caused. The full effect of the mixtures isattained at temperatures above C., so that anti-oxidizers must be usedto prevent possible oxidations taking place at these high temperatures.In the dyeing of polyamide fibers with complex metal dyestuffs andreactive dyestuffs, fabric irregularities cannot be levelled outsatisfactorily and a strong retardative effect is observed with somedyestuffs. A drawback is also the necessity of exactly adjusting thepH-value of the dyebath for obtaining optimum effects.

It is an object of this invention to provide an improved process for themore complete dyeing of textile materials having a basis of a syntheticlinear polyamide with a dyestuff for said material. Another object ofthis invention is the provision of an aqueous dyebath comprising an aciddyestuff, a complex metal dyestuff, a reactive dyestuff or a mixturethereof and a particularly effective dyeing assistant. Other objects ofthis invention will be apparent from the following detailed descriptionand claims:

We have found that streak-free dyeings on textile materials having abasis of a synthetic linear polyamide with acid dyestuffs as well aswith complex metal dyestuffs and reactive dyestuffs are obtained, whencarrying out the dyeing in the presence of a colorless compound of theformula (I) if desired or required, together with a weaklycation-active, complex-forming agent.

In the above Formula I R represents hydrogen or a low molecular alkylradical,

A represents an aliphatic, aromatic, araliphatic, or cycloaliphaticradicals,

Z represents an anion-active group such, for example, as SO Y, -OSO -,Y,-COOY, -SO CH CH OSO Y (Y=hydrogen or a salt forming cation, preferablyan alkali metal cation),

n represents an integer from 1 to 3,

X represents halogen, preferably chlorine or the group wherein R, A, Zand n have the meanings given above. As compounds of the Formula I,there are preferably used compounds in which R represents a hydrogenatom,

A represents an alkylene radical having 1-4 carbon atoms,

a phenylene radical, a naphthalene radical or a phenylene or naphthaleneradical substituted by one or several nitro groups, amino groups, lowmolecular alkyl or alkoxy radicals, and/or halogen, and Z, n and X havethe meanings given above.

The compounds of the present invention permit dyeing at temperatures ofup to 130 C. without the addition of protective agents and withoutincurring the risk of damaging the fibres. By application of this hightemperature, in many cases the yield and the levelness are ratherimproved.

Another advantage in the use of the assistants of the present inventionis that dull shades on polyamide textiles are obtained, since inpractice the luster of the dyed goods has always been objected to.

The assistants having the Formula I can be prepared, for example, byreacting amines of the formula NH'A' '(Z)n with cyanuric chloridepreferably in an aqueous medium, at a reaction temperature ranging fromto 100 C., while neutralizing the hydrogen chloride liberated.

As neutralizing agents, there may be preferably used mineralacid-binding agents, for example, alkali metal hydroxides, carbonates orhydrogen carbonates, and alkaline earth metal hydroxides, carbonates orhydrogen carbonates.

As amines of the general formula there may be used:

The 2,4,6 s triazine tri aminobenzene fi hydroxyethylsulfone sulfuricacid esters can also be prepared by reacting cyanuric chloride withaminobenzenefl-hydroxyethylsulfone in the melt or in a higher-boilingorganic solvent, for example, xylene and subsequent esterification ofthe trihydroxy compound formed with concentrated sulfuric acid.

As complex-forming, weakly cation-active products which may be used, ifrequired or desired, together with the compounds of the Formula I, thereenter into consideration, for example, the addition products of alkyleneoxide to alkylamines or polyalkylene polyamines, prefearably thecompounds obtained by the addition of 2-30 mols of ethylene oxide to 1mol of an alkylamine having at least one alkyl radical with 8-18 carbonatoms or of a substituted alkylamine, for example, a compound of theformula in which R stands for alkyl radical having 8-18 carbon atoms, or1 mol of a polyalkylene polyamine such as ethylene diamine, diethylenetriamine or hexamethylene diamine; condensation products of melamine,formaldehyde and one compound obtained by the addition of prefer-ably8-80 mols of ethylene oxide to 1 mol of triethanolamine, or the productsobtained by acid condensation of formaldehyde and addition products ofalkylene oxide, preferably of 8-50 mols of ethylene oxide to 1 mol of amixture of a simple aromatic amine such, for example, as aniline and aphenol, and, if required or desired, a low molecular alkanolamine,especially triethanolamine. Furthermore, there may be used thequaternization products of the above-specified compounds, for example,those obtained by the reaction with dimethyl sulfate.

The ratio of the anion-active to the cation-active compound used ifdesired or required, can vary within wide limits. Thus, as has alreadybeen mentioned, the anionactive compounds encompassed by the Formula Imay be used with good results alone. When mixtures of the mentionedanion-active and cation-active compounds are used, the ratio of theindividual components may be adjusted to the prevailing circumstances ofeach individual case. The components can be used in equal amounts, butit generally proved advantageous to use an excess of anionactivecompound. It is preferred to use a ratio of 3 parts by weight ofanion-active compound to 1 part by weight of cation-active compound.

For stabilization, there may be added to the mixtures of anion-activeand cation-active compounds, if desired or required, about 0.5-2% of anon-ionic surface-active compound, for example, the product obtained bythe addition of 20-40 mols of ethylene oxide to 1 mol of an alkyl phenolhaving an alkyl radical with about 8-12 carbon atoms.

The dyeing conditions, such as the dyebath temperature, the pH of thedyebath, the proportion of dyestuff in the dyebath and the liquor ratio,may be varied as desired. Thus the dyebath is preferably heated to atemperature of at least to C.; mostly, the dyeing is carried out at thenormal boiling point of the dyebath. Augmentation of the dyeingtemperature to about l20130 C. is possible, but is in most cases notnecessary to obtain streakless dyeings with good depth of shade. Thedyebath should have an acid pH. The pH value may range between about 3and 6, preferably between 3 and 4.

In comparison with the quantity used of other known assistants, thesmall quantity of 0.5-3 percent by weight of the anion-active dyeingassistant or of the mixture of anion-active and cation-active substancesaccording to the invention, which gives good results even with deepshades, is a considerable advantage. In many cases, a quantity of only0.5-2 percent by weight, referred to the weight of the goods, willalready be sufiicient.

When using the compounds or mixtures according to the present invention,streakless, level dyeings on polyamide fibrous materials will beobtained. Changes of the depth of shade and of the shade itself do notoccur or only in a practically insignificant degree. The drawbacks ofthe known processes are thereby obviated.

Furthermore, when using the products in the dyeing of polyamide fiberswith acid wool dyestuffs, good wetting and rubbing fastnesses areobtained. Especially good results will in this case be obtained whenusing as anionactive compounds of the Formula I such as contain thegroup SO CH CH -OSO Y (Y having the meaning given in Formula I andrinsing the goods after dyeing for 1 to 20 minutes at temperatures inthe range of 60 and 90 C. with an aqueous alkaline bath in the presenceof a high molecular compound containing at least 3 hydroxyl groups.During this treatment in the alkaline medium, there form reactivevinylsulfone groups in the anion-active dyeing assistant which causecross-linking with the added compounds containing hydroxy groups. Thisfastnessimproving treatment can also be carried out by padding withalkalies and compounds containing hydroxyl groups the dyeings producedon polyamide fabrics in the presence of compounds of the Formula Icontaining the group -SO CH CH -OSO Y and then further treating thefabric as usual on the stenter at temperatures in the range of 90 and180 C. for a period from 30 seconds to 10 minutes.

As alkalies for the aftertreatment, there may be used in particularalkali metal hydroxides, alkali metal carbonates and alkali metalbicarbonates, as well as alkali metal salts of organic acids which passover into hydroxides or carbonates at elevated temperatures. There arementioned by way of example: sodium hydroxide, potassium hydroxide,sodium carbonate, potassium carbonate, and the correspondingbicarbonates, sodium acetate, potassium acetate as well as the sodium orpotassium salt of trichloroacetic acid.

The alkalies are generally used in amounts from about 0.3 to 10 percentby weight, preferably 0.3 to 5 percent by weight, referred to the weightof the goods. The quantity should be so chosen as to give a pH of atleast 8. If compounds are used, which pass into alkalies at elevatedtemperatures, for example, the sodium salt of trichloroacetic acid, onecan work under neutral or weakly acid conditions.

As higher molecular compounds of synthetic origin, with alcoholichydroxyl groups, there enter into consideration for example, polyvinylalcohols having K-values from about to 100 (according to Fickentscher,Cellulosechemie, tome 13, page 58 (1932)), polyvinyl alcohols which canbe either fully hydrolyzed or partly hydrolyzed and have a residualacetyl content of 090% as well as polyvinyl acetals containing hydroxylgroups, i.e. partly acetalized polyvinyl alcohols, for example,acetalized with formaldehyde, acetaldehyde, benzaldehyde or otheraliphatic or aromatic aldehydes, with an acetalization degree of 099%and K-values from 10 to 100. Furthermore, copolymers of monomeric vinylcompounds such as vinyl chloride, acrylic acid esters, methacrylic acidesters, acrylonitrile, styrene, etc. with vinyl esters such as vinylformiate, vinyl acetate, vinyl propionate, etc., into which hydroxylgroups have been introduced by partial hydrolysis. The proportion ofvinyl ester groups in the mentioned copolymers can vary between 0.5 and99%, the degree of hydrolyzation of the vinyl ester component can varyfrom about 10 to 100%. Furthermore, there are also suitable resins orpartially hydrolyzed graft polymers of vinyl esters with polyethyleneglycols, for example, those obtained according to the Germanspecifications 1,081,229 and 1,094,457.

As hydroxyl-containing compounds of natural origin there may be usedinter alia carbohydrates such as starches (wheat starch, rice starch,potato starch, etc.) tragacanth, tannine, locust bean flour as well aslocust bean flours that are partially etherified with lower, monoordihydric aliphatic alcohols having 14 carbon atoms, modified star-chpreparations for example, British rubber, sugar, and sugar alcohols,furthermore cellulose esterified with lower carboxylic acids or loweralcohols having 14 carbon atoms or etherified cellulose, for example,methyl cellulose, carboxymethyl cellulose, etc.

The following examples illustrate the invention, but they are notintended to limit it thereto:

Example 1 I 100 parts of a polyamide fabric consisting in warp and beamof endless filaments, normally dyeing 'with streaks only, are dyed in aclosed dyeing apparatus for 1 hour at 100 C. with 2 parts of an acidwool dyestuff strongly responding to yarn irregularities and having thegeneral formula 1000 parts of water, after having brought the dyebath tothe above temperature in the course of 40-50 minutes. After rinsing anddrying, there is obtained a streakless, fast, grey dyeing.

An improved fastness can be obtained, when treating the goods in thefirst rinsing bath with 2 parts of sodium trichloroacetate, or 2 partsof sodium bicarbonate alone or together with 2 parts of tannine, for 20minutes at 60-80 C.

Equally good results are obtained when carrying out the process with 2parts of a sodium hydroxide solution (32.5%) at 20 C.

The described aftertreatment can be carried out by padding on a foulardand drying the dyed fabric on a stenter for 5 minutes at 140 C.

In each case, dull colored goods having a convenient handle areobtained.

Example 2 parts of the fabric described in Example 1 are dyed asdescribed in Example 1 with a dyebath having the following composition:

3 parts of the acid wool dyestufi of the constitution Example 3 100parts of the polyamide fabric which can be dyed with streaks only andwhich is described in Example 1,

3 parts of 2,4,6-tri- (1-aminobenzene-3potassium sulfonate)-s-triazine,1 part of the condensation product from 6 mols of formaldehyde, 1 mol ofmelamine and 1 mol of the product of the addition of 30 mols of ethyleneoxide to 1 mol of triethanolamine, prepared by condensation in an acidmedium, and subsequently quaternized with dimethyl sulfate, 0.75 part ofthe product of the addition of 30 mols of ethylene oxide to 1 mol ofnonyl phenol (30% strength), 3 parts of acetic acid (30% strength), 1000parts of water, in a closed dyeing apparatus, while bringing the bath tothe above temperature of 100 C. in the course of 1 hour, dyeing for 45minutes at this temperature and finally dyeing for 15 minutes at 120 C.

After rinsing and drying, there is obtained a streakless, orange dyeinghaving good fastness properties.

Instead of the above described cation-active product, there can be usedwith the same success 1 part of a compound obtained by heating 213 g. ofthe product of the addition of 616 g. (14 mols) of ethylene oxide to 93g. (1 mol) aniline with 28.2 g. of phenol and 60 cc. of formaldehydesolution of 30% strength in the presence of 40 cc. of sulfuric acid of64% strength, while stirring and in the course of 50 minutes, to 100105C., adjusting the pH-value of the solution to 9 by adding sodiumhydroxide solution, and methylating the condensation prodnot at 5060 C.by adding 91 g. of dimethyl sulfate, whereupon 291 g. of the quaternarycondensation product are obtained in the form of a solution.

Example 4 100 parts of the polyamide fabric described in Example 1 whichcan be dyed with streaks only are dyed under the conditions described inExample 1 with a dyebath having the following composition:

2 parts of the reactive dyestuff of the constitution 3 parts of 2,4,6tri- (1 aminobenzene-3-potassium sulfonate)-s-triazine, 1 part of thecondensation product from 12 mols of ethylene oxide and 1 mol ofstearylamine (30% 2 parts of acetic acid (30% strength), 1000 parts ofwater.

After rinsing and drying, there is obtained a streakfree fast yellowdyeing corresponding in depth of shade and shade to an untreated dyeing.

Example 5 parts of the fabric of polyamide described in Example 1, whichcan be dyed with streaks only, are dyed with a combination of aciddyestuffs of 4 parts of the red dyestuff A, 3.6 parts of the yellowdyestuff B, 0.05 part of the blue dyestulf C.

1.6 parts of 2,4,6-tri-(1-aminobenzene-3-potassiumsulfonate)-s-triazine, 0.5 part of the condensation product of 12 molsof ethylene oxide and stearyl amine (30%), 3 parts of acetic acid (30%strength), and 1000 parts of water for 1 hour at 100 C., rinsed anddried.

There is obtained a red, streakfree and level dyeing corresponding to anuntreated dyeing with regard to depth of shade and shade.

Instead of 1.6 parts of 2,4,6-tri-(1-aminobenZene-3- potassiumsulfonate)-s-triazine, there may also be used 1.6 parts of2,4,6-tri-(l-aminobenzene 2 sodium sulfonate)-s-triazine.

Example 6 100 parts of the fabric described in Example 1 are dyed, aftersingeing, for 10 minutes at 30 0., with a bath having the followingcomposition:

1000 parts of water, 3 parts of 2,4,6-tri-( l-naphthylamino-3,6-disulfonic acid)-s-triazine, 1 part of the compound CHzC1o 1 (Rmeaning soya bean oil), 0.25 part of a nonyl phenol oxethylated with 20mols of ethylene oxide, and 3 parts of ace i a id (30% strength).

9 To the dyebath are then added through a sieve 3 parts of the complexchrome 2:1 dyestutr of 2 molecules of the following composition asaqueous solution, the Whole is heated within 30 minutes to 100 C. anddyeing is carried out for 60 minutes at this temperature.

The dyed goods are then rinsed and dried. There is obtained a level greydyeing.

Without the addition of the dyeing assistant, the nodules formed by thesingeing would be dyed deeper owing to their greater afiinity for thedyestuif than the fabric.

Example 7 100 parts of the fabric described in Example 1 are dyed for 15minutes at 30 C. with a bath having the following composition: 1000parts of water, 3 parts of 2,4,6-.tri-(1-aminobenzene-2,4-disulfonicaoid)-s-triazine, 1 part of the condensation product of 6 mols ofethylene oxide and 1 mol of laurylamine, and 3 parts of acetic acid (30%strength).

2 parts of the dyestulf of the formula sO Na in which R is a memberselected from the group consisting of hydrogen and a low molecular alkylradical, A is a member selected from the group consisting of an alkyleneradical having 1-4 carbon atoms, a phenylene and naphthylene radical, asubstituted phenylene and a substituted naphthylene radical, Z is amember selected from the group consisting of SO Y, -OSO Y, COOY, and SOCH CH OSO Y (Y being a member selected from the group consisting ofhydrogen and a salt-forming cation) and n is an integer from 1 to 3, asan assistant for levelling the dyeing.

2. The process as defined in claim 1, in which 2,4,6- tri-(l-aminobenZene-4-sodium sulfonate)-s-triazine is used as the assistantfor levelling the dyeing.

3. Process for dyeing textile materials having a basis of a syntheticlinear polyamide, which comprises bringing said textile materials intocontact with an aqueous dye- 10 bath containing an acid wool dyestuff inthe presence of a colorless compound of the formula i Z n-AN(;J \(IJNAZn N\ /N C in which R is a member selected from the group consisting ofhydrogen and a low molecular alkyl radical, A is a member selected fromthe group consisting of an alkylene radical having 1-4 carbon atoms, aphenylene and a naphthylene radical, a substituted phenylene and asubstituted naphthylene radical, Z represents the group SO CH CH OSO Y(Y being a member selected from the group consisting of hydrogen and asalt-forming cation) and n is an integer from 1 to 3, as an assistantfor levelling the dyeing, and rinsing the dyed materials in an aqueousalkaline bath containing a high molecular compound having at least 3hydroxyl groups.

4. The process as defined in claim 1, in which the compound of theformula is used as the assistant for levelling the dyeing.

5. Process for dyeing textile materials having a basis of a syntheticlinear polyamine, which comprises bringing said textile materials intocontact with an aqueous dyebath containing a dyestuff for said materialsin the presence of a colorless compound of the formula RI IAZu in whichR is a member selected from the group consisting of hydrogen and a lowmolecular alkyl radical, A is a member selected from the groupconsisting of an alkylene radical having 1-4 carbon atoms, a phenyleneand a naphthylene radical, a substituted phenylene and a substitutednaphthylene radical, Z is a member selected from the group consisting of--SO Y, COOY, and SO CH CH OSO Y (Y being a member selected from thegroup consisting of hydrogen and a salt-forming cation) and n is aninteger from 1 to 3, and a complexforming weakly cation-active productas assistants for levelling the dyeing.

6. A process as defined in claim 5, wherein the complex-forming Weaklycationic active product is an addition product of 2 to 30 mols ofethylene oxide per mol of an alkylamine having an alkyl radical with 8to 18 carbon atoms.

7. The process as defined in claim ll wherein the assistant forlevelling the dyeing is 2,4,6-tri-(l-aminobenzene- 3-potassium sulfonates-triazine.

8. The process as defined in claim 1 wherein the assistant for levellingthe dyeing is 2,4,6-tri-(l-naphthylamino- 3,6-disulfonicacid)-s-triazine.

9. The process as defined in claim ll wherein the assistant forlevelling the dyeing is 2,4,6-tri-(l-aminobenzene- 2,4-disulfonicacid)-s-triazine.

References Cited by the Examiner UNITED STATES PATENTS 3,054,699 9/1962Moyse 8-18 NORMAN G. TORCHIN, Primary Examiner.

J. HERBERT, Assistant Examiner.

1. PROCESS FOR DYEING TEXTILE MATERIALS HAVING A BASIS OF SYNTHETICLINEAR POLYAMIDE, WHICH COMPRISES BRINGING SAID TEXTILE MATERIALS INTOCONTACT WITH AN AQUEOUS DYEBATH CONTAINING A DYESTUFF FOR SAID MATERIALSIN THE PRESENCE OF A COLORLESS COMPOUND OF THE FORMULA